CN1426430A - Thermoplastic polyurethane elastomers (TPUs) prepared with polytrimethylene carbonate soft segment - Google Patents

Thermoplastic polyurethane elastomers (TPUs) prepared with polytrimethylene carbonate soft segment Download PDF

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CN1426430A
CN1426430A CN01808410A CN01808410A CN1426430A CN 1426430 A CN1426430 A CN 1426430A CN 01808410 A CN01808410 A CN 01808410A CN 01808410 A CN01808410 A CN 01808410A CN 1426430 A CN1426430 A CN 1426430A
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tpus
glycol
composition
hard segment
ptmc
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CN1177880C (en
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W·H·布恩
T·C·福施尼尔
K·C·福里施
D·E·格维恩
A·森狄雅勒维克
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Shell Internationale Research Maatschappij BV
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

A thermoplastic polyurethane elastomer (TPU) composition which comprises: a) a poly(trimethylene carbonate) diol (PTMC diol) as the soft segment; b) a diisocyanate; and c) at least one glycol which reacts with the diisocyanate to form the hard segment which comprises from 10 % to 55 % by weight of the composition wherein the hard segment is defined as the sum portion of diisocyanate that reacts with the glycol plus the unreacted glycol.

Description

Utilize the Polyurethane Thermoplastic Elastomer (TPUs) of polytrimethylene carbonate soft chain segment preparation
Invention field
The present invention relates to Polyurethane Thermoplastic Elastomer (being called TPUs hereinafter).More particularly, the present invention relates to utilize the class new TP Us of polytrimethylene carbonate glycol (PTMC glycol) as the soft chain segment preparation.Utilize the TPUs dibasic alcohol chain extension of PTMC glycol preparation, described dibasic alcohol is preferably and hangs down the functionality dibasic alcohol, for example comprises 1, ammediol and 1,4-butyleneglycol.
Background of invention
TPUs is important technically, because they combine the known advantage of high-quality mechanical property and cheap thermoplastics processibility.By utilizing different chemical compositions can on mechanical property, obtain multiple variation.For example at Polyurethane Handbook (polyurethane handbook), G ü nter oertel edits, Hanser Publishers, and Munich has described testing method, its performance and the application of TPUs in 1985, the 405-417 pages or leaves.
TPUs is by linear polyvalent alcohol, is generally polyester or polyether glycol, organic diisocyanate and short chain dibasic alcohol (chain extension agent) and constitutes.The overall performance of TPU will depend on the structure of type, its molecular weight, isocyanic ester and the chain extension agent of polyvalent alcohol, and the ratio of soft chain segment and hard segment.
Urethane can be thermoplastic also can be heat cured, this depends on crosslinked degree.Thermoset and thermoplastic polyurethane can be made by " single stage method " between isocyanic ester and polyvalent alcohol reaction, also can make by " prepolymer " system, wherein, solidifying agent is joined in the polyvalent alcohol-isocyanic ester mixture of partial reaction and finish polyurethane reaction.Do not exist elementary crosslinkedly in the thermoplastic polyurethane, and there be in various degree crosslinked in heat-curable urethane according to the difference of reactant functionality.
Thermoplastic polyurethane is normally based on methylene diisocyanate (MDI) or tolylene diisocyanate (TDI), and not only comprised the polyvalent alcohol of polyester grade but also comprised the polyvalent alcohol of polyethers level.In order to adjust its performance, polyvalent alcohol, chain extension agent and vulcabond component can change in relative wide molar ratio range.
In order to improve processing characteristics, particularly for by extruding product processed, the stability of raising and adjustable melt flow rate (MFR) are very important.This depends on chemistry and the morphological structure of TPUs.Improve the needed structure of processing characteristics usually by using chain extension agent mixture for example 1,4-butyleneglycol/1, the 6-hexylene glycol is realized.As a result, the arrangement of hard segment distortion so big so that, not only melt flow rate (MFR) has improved, and simultaneously, thermomechanical property for example tensile strength and heat-resistant deforming performance suffers damage usually.
All there are some defectives in known TPUs and the mixture that contains TPUs in comprising mechanical property, one or more performances of colour stability, transparency, thermal distortion and being separated property to photo-thermal.Improve a kind of performance for example the method for hardness often cause the degeneration of another kind of performance.
Therefore, at TPUs and containing in the mixture of TPUs, in the heat-drawn wire that reaches hardness and relevant mechanical property, stable color, transparency and Geng Gao, have problems.Therefore, a kind of new TPUs prescription need be developed in this area, obtains the mechanics of wide region more and thermal characteristics and the already present performance that do not reduce.
The present invention is utilizing known thermoplastic material, is being useful by providing a kind of new TP Us to overcome in one or more problems, this TPUs has been for the mechanics and the thermal characteristics of TPU prescription provide new possibility, comprises improving the transparency, hardness, higher Young's modulus and improved softening temperature and thermal expansivity.
Summary of the invention
The invention provides a kind of new TP Us that improves performance, it is based on poly-(1, the ammediol carbonic ether) glycol (PTMC glycol), and having hard segment, described hard segment comprises the isocyanic ester and the dibasic alcohol part and the vulcabond that solidifies this system that are blended among the TPU with diol reaction.This elastomerics is than more or less harder based on the corresponding TPUs of polyvalent alcohol well known in the art.This PTMC TPUs has good physical and mechanical properties, comprises the Young's modulus more or less higher than reference TPU.S compares with polyether TPU, and its wear resistance and compression set are also very good.Have found that its softening temperature and thermal expansivity also have improvement than reference TPUs.In addition, utilize the PTMC polyvalent alcohol, can improve the transparency of TPUs, and in certain embodiments, even can access complete material transparent.
According to top described, the present invention includes Polyurethane Thermoplastic Elastomer (TPU) composition, it comprises:
A) as poly-(propylene carbonate) glycol (PTMC glycol) of soft chain segment;
B) vulcabond; With
C) at least a dibasic alcohol (being called chain extension agent sometimes), it and di-isocyanate reaction form the hard segment that accounts for composition 10-55% weight, and wherein, hard segment is defined as the summation part with the vulcabond and the unreacted dibasic alcohol of diol reaction.
Brief description of drawings
Below, the present invention will be with reference to the accompanying drawing of back, be described by embodiment, wherein:
Fig. 1 is the graphic representation of expression polycarbonate polyol viscosity;
Fig. 2 be the expression based on 1, the 4-butyleneglycol (1, the bar graph of the stress of TPUs 4-BD) when 100% strain;
Fig. 3 represents based on 1 the bar graph of the stress of the TPUs of 4-BD when 300% strain;
Fig. 4 be expression based on 1, ammediol (1, the bar graph that the tensile strength of TPUs 3-PDO) keeps;
Fig. 5 is the bar graph that two all backs changes in weight in 70 ℃ of water are immersed in expression;
Fig. 6 represents initial and the bar graph that immerses the tensile strength after two weeks in 70 ℃ of water;
Fig. 7 is that all backs chemical-resistant bar graph is immersed in expression.
Detailed description of the present invention
Among the present invention, utilize poly-(propylene carbonate) glycol as soft chain segment, the hard segment that contains dihydroxylic alcohols, preferred short chain dihydroxylic alcohols and vulcabond has prepared novel thermoplastic polyurethane (TPUs). Suitable poly-(propylene carbonate) glycol is to prepare by the method that the following describes, and the sample characteristic that uses in the embodiment of the invention is that molecular weight is about 2000. Estimated the performance based on the TPUE of PTMC glycol.
Preparation has also been estimated aromatics and alicyclic TPUs based on the PTMC glycol. With 4,4 '-methyl diphenylene diisocyanate (MDI) preparation aromatics TPUs, and with methylene-two (4-cyclohexyl isocyanate) (H12MDI) preparation aliphatic TPUs. Elastomer utilizes the one-step method preparation. In embodiment 2,3,5 and 10, use 1,3-PDO and Isosorbide-5-Nitrae-BD to make cahin extension agent, and in an embodiment, the concentration of hard segment change to 35% from 22%. In order to make comparisons, to prepare and estimated TPUs based on the representative polyalcohol of commercially available poly-(1,6-hexylene glycol carbonic ester) glycol (available from the Desmophen C-200 of Bayer Co.) and this area use.
The physical and mechanical properties (hardness, stress-strain property, resistance to tearing, compression set, elasticity and wearability) of TPUs has been tested in standard method according to ASTM. Solvent resistance (paraffin oil, ethylene glycol and diluted acid/diluted alkaline) is determined by the rear changes in weight of test dipping. Resistance to water is to be immersed in behind 70 ℃ of water retentivity and the changes in weight of stress-strain property by test to estimate.
Elastomeric form is by the heat analysis and research, and described heat analysis comprises differential scanning calorimetry (DSC), thermodynamic analysis (TMA) and dynamic mechanical analysis (DMA) and Fourier transform infrared analysis (FTIR). The elastomeric transparency is tested by the light transmittance (%) of test in the visible-range of 474-630 nanometer.
Because the rigidity of PTMC glycol, elastomer shows relatively high Tg (being about 0 ℃). Their hardness ratio is more or less higher based on the corresponding TPUs of for example Desmophen C-200, PolyTHF (PTMO) 2000 or caprolactone polyol (referring to table 17 and 18).
PTMC 2000 TPUs have good physical and mechanical properties.The height of their modular ratio Desmophen C-200 TPUs.Wear resistance and the compression set of TPMC 2000 TPUs are very good, can compare favourably with polyether TPU s.
Shown in high-temperature behavior, thermostability, softening temperature and the thermal expansivity of discovery PTMC 2000 TPUs increases than the performance of Desmophen C-200 TPUs.By using PTMC 2000, can improve the transparency of TPUs, utilize H 12MDI even can access complete material transparent.
The oil-proofness excellence of PTMC 2000 TPUs, for example the resistivity of diluted mineral acid, mineral alkali and ethylene glycol is also fine to other medium.
Poly-(propylene carbonate) polyvalent alcohol
Although can use the polyvalent alcohol of high functionality to prepare the thermoset system usually, TPUs of the present invention has utilized PTMC glycol, dibasic alcohol and the vulcabond with the particular form preparation in an embodiment.The PTMC glycol is to prepare according to method described in our the common pending application PCT/EP01/02323.Wherein said PTMC glycol is a feature to have improved the transparency, and end group all is a hydroxypropyl basically, does not have the allyl group that can test.
For the performance for preparing with these needs is the polytrimethylene carbonate of feature, with propylene carbonate in the presence of catalyzer, preferably under nitrogen atmosphere with polyol reaction.This polyvalent alcohol can be glycol or triol or more polyvalent alcohol, for example propylene glycol and TriMethylolPropane(TMP) or their mixture.
Propylene carbonate can prepare under the catalyzer not having.Yet catalyzer provides shorter advantage of reaction times.Appropriate catalyst is selected from the salt of IA family in the periodic table of elements or IIA family.Utilize sodium acetate to receive good effect.Although IA family or the common consumption of IIA family catalyzer can be 5-1000ppm, preferably about 10-100ppm, 10-40ppm most preferably from about, a small amount of just effectively, from less than 1ppm to greater than 10,000ppm.
Although can use solvent, preferably do not use solvent to prepare polytrimethylene carbonate.
Polytrimethylene carbonate is in the preparation of 50-160 ℃ temperature.Preferred temperature is 100-150 ℃, most preferably 110-130 ℃.Pressure is unimportant, in fact, almost can use any pressure, but has received good effect under the normal pressure.
The performance of polytrimethylene carbonate is by the Several Factors decision, and most important factor is the consumption and the kind of any initiation alcohol, catalyzer and catalyst levels and processing condition.The manufacturer can change determinative in advance in order to prepare the needed molecular weight of final application, polydispersity coefficient and further feature.
Among the present invention, in order to prepare the new TP Us of the formulation selection that provides new, utilize the PTMC glycol to obtain good effect, wherein said PTMC glycol prepares according to the method described above, and it is about 10,000 that molecular weight is lower than, and is preferably 1000-3000.The TPUs that uses among this paper embodiment is to be 2000 PTMC glycol preparation with molecular weight.
Dibasic alcohol (chain extension agent)
Diol component can be selected from aliphatic series, alicyclic, aralkyl and aromatic diol.Just as is known to the person skilled in the art, high functionality alcohol can be used for multiple use.Yet the present invention utilizes low functionality dibasic alcohol to obtain good effect.The example of the dibasic alcohol of enumerating includes, but are not limited to ethylene glycol, propylene glycol, 1, ammediol, the 2-methyl isophthalic acid, ammediol, 2,4-dimethyl-2-ethyl hexane-1,3-glycol, 2,2-dimethyl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 2-ethyl-2-isobutyl--1, ammediol, 1,3 butylene glycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 2,2,4-trimethylammonium-1, the 6-hexylene glycol, the sulphur di-alcohol, 1, the 2-cyclohexanedimethanol, 1, the 3-cyclohexanedimethanol, 1, the 4-cyclohexanedimethanol, 2,2,4,4-tetramethyl--1,3-cyclobutanediol and to xylenediol, or their mixture.Other example of suitable dibasic alcohol comprises the hydroxyalkyl derivant of the promptly two 2-hydroxyethyl ethers (HQEE) of the hydroxyalkyl derivant of quinhydrones and Resorcinol and dihydroxyphenyl propane.This dibasic alcohol is preferably selected from 1, ammediol and 1,4-butyleneglycol or their mixture.Embodiment 2,3,5 and 10 has illustrated 1, ammediol and 1, the application of 4-butyleneglycol.
Hard segment content is and the isocyanic ester of diol reaction and the summation of unreacted dibasic alcohol part.Blend dibasic alcohol hard segment in TPU, in an amount equivalent to 10-55% hardkey section content, preferred 20-40% hard segment content.
Isocyanic ester
Be used for the elastomeric isocyanic ester of curing urethane and generally include aliphatic series, aromatics or alicyclic polyisocyanates.In order to prepare TPUs of the present invention, used vulcabond.Suitable vulcabond is aliphatic series, aromatics or alicyclic diisocyanate.The example of aliphatic vulcabond is a hexamethylene diisocyanate.The example of alicyclic diisocyanate comprises isophorone diisocyanate, 1,4-cyclohexyl diisocyanate, 1-methyl-2,4-and-2,6-cyclohexyl diisocyanate and corresponding isomer mixture, 4,4 ', 2,4 ', with 2,2 '-dicyclohexyl-methane diisocyanate and corresponding isomer mixture.The example of aromatic diisocyanate comprises 2,4 toluene diisocyanate, 2,4-and 2, the mixture of 6-tolylene diisocyanate, 4,4 ', 2,4 '-and 2,2 '-diphenylmethanediisocyanate, 2,4 '-and 4, the mixture of 4 '-diphenylmethanediisocyanate, urethane-modified liquid 4,4 '-and/or 2,4 '-diphenylmethanediisocyanate, 4,4 '-two isocyanato-diphenylethanes-(1,2) and 1,5-naphthalene diisocyanate.The example of the vulcabond that other is suitable comprises, but be not limited to diphenylene-4,4 '-vulcabond, 3,3 '-dimethoxy-4 ', 4 '-diphenylene vulcabond, methylene radical-two-(4-cyclohexyl isocyanate), tetramethylene diisocyanate, the decamethylene vulcabond, ethylidene diisocyanate, ethylidene diisocyanate, propylidene-1, the 2-vulcabond, cyclohexylidene-1, the 2-vulcabond, the metaphenylene vulcabond, to phenylene vulcabond, 3,3 '-dimethyl-4,4 '-diphenylene vulcabond, 3,3 '-dimethoxy-4 ', 4 '-diphenylene vulcabond, 3,3 '-phenylbenzene-4,4 '-diphenylene vulcabond, 4,4 '-diphenylene vulcabond, 3,3 '-two chloro-4,4 '-diphenylene vulcabond, the furfurylidene vulcabond, xylylene diisocyanate, diphenyl propane-4,4 '-vulcabond, two-(2-isocyanatoethyl) fumarate, naphthalene diisocyanate and their mixture.
Other diisocyanate cpd for example can comprise 1,4 '-dicyclohexyl methane diisocyanate, 3-isocyanato-methyl-3,5,5-3-methyl cyclohexanol based isocyanate, cyclohexylidene-1, the 4-vulcabond, 4,4 '-methylene-bis (phenyl isocyanate), 2,2-diphenyl propane-4,4 '-vulcabond, to phenylene vulcabond, the metaphenylene vulcabond, Xylene Diisocyanate, 1, the 4-naphthalene diisocyanate, 4,4 '-biphenyl diisocyanate, nitrogen benzide-4,4 '-vulcabond, between or to tetramethylxylene diisocyanate and 1-chlorobenzene-2,4-vulcabond, hexamethylene diisocyanate, 4,6 '-Xylene Diisocyanate, 2,2,4-(2,4,4-) trimethyl hexamethylene diisocyanate, 3,3 '-dimethyl diphenyl-4,4 '-vulcabond, 3,3 '-dimethyl-ditan 4,4 '-vulcabond, etc.
Be used for illustrating that the preferred vulcabond that the embodiment of beneficial effect of the present invention uses is 4,4 '-diphenylmethanediisocyanate (MDI) and methylene radical-two (4-cyclohexyl isocyanate) (H 12MDI).
Catalyzer
When using catalyzer, appropriate catalyst is that those quicken the catalyst for reaction between the hydroxyl of the NCO group of vulcabond and structural constituent.The example comprises tertiary amine well known in the art and organometallic compound, and for example is disclosed among the US-A-6022939.Illustrate, suitable compound comprises triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N '-lupetazin, 2-(dimethylamino oxyethyl group) ethanol and diazabicylo (2,2,2) octane and their mixture, and organometallic compound for example titanic acid ester, iron cpd and tin compound, the example comprises the dialkyltin salts of oxalic acid tin, two stannous octoates, two lauric acid tin and aliphatic carboxylic acid, for example dibutyltin diacetate and dibutyl tin laurate or their mixture.Usually use 0.0005-0.5 part catalyzer in per 100 parts of polyols.
Preparation
TPUs of the present invention prepares by single stage method.Among the embodiment, the concentration that is included in the hard segment in the PTMC urethane is about 10-55%, preferred 20-40% weight.
The isocyanic ester coefficient, i.e. isocyanic ester and hydroxyl equivalent ratio depend on the isocyanic ester and the dibasic alcohol (generally being called chain extension agent) of use.For thermo-setting elastomer, this coefficient is generally 0.105-600, or bigger.Among the present invention, different according to prescription, the isocyanic ester coefficient is 0.8-1.04.But it is preferred near about 1.02.
With polyvalent alcohol and dibasic alcohol (chain extension agent) at 70-150 ℃, preferred 95-140 ℃ of heating down, in the specific embodiment 100-135 ℃ of heating down.Can use higher slightly temperature, but as known in the art,, not advise so usually for fear of side reaction.With vulcabond preheating under mixing temperature, join in polyvalent alcohol and the chain extension agent mixture, and all components is acutely mixed 5-10 second.Then mixture is poured on the mould that the teflon of preheating covers (＜150 ℃).Determine gelification by the one-tenth silk (string formation) that about 10-20 took place in second,, mould be placed in the Carver press as when silk, and with this resin in the mold of contracting of the temperatures of elevated pressure and medium rising.Pressure be preferably 137.9-206.8MPa (20,000-30,000psi), suitable temperature is 100-140 ℃.As is known to the person skilled in the art, suitable pressure also can be higher or lower than this scope.Subsequently, with polyurethane sheet at 90-150 ℃, post-hardening in the preferred 100-140 ℃ of baking oven, setting time can be several hours to several days according to temperature.
The embodiment of back will be used to illustrate the specific embodiment of the present invention disclosed herein.These embodiment only are the modes of thinking as an illustration, and limit the scope of the invention anything but.Those skilled in the art can make multiple variation to it under the prerequisite that does not depart from spirit of the present invention.
Embodiment
The material that uses among the embodiment is shown in Table 1.Former state from supplier since the isocyanic ester is used.Its NCO% concentration is to test by titration according to the Di-n-Butyl Amine method of ASTM D1638-74.The hydroxyl groups number is tested by standard Tetra hydro Phthalic anhydride esterification process (ASTM D4273).
Table 1 raw material
Material Chemical ingredients Equivalent (Eq.Wt.) Supplier
Glycol PTMC 2000 (24288-96) PTMC 2000 (24617-12B) Desmophen C-200 cahin extension agent (dihydroxylic alcohols) 1; 3-PDO Isosorbide-5-Nitrae-BD vulcabond Desmodur M Desmodur W Poly-(1, the ammediol carbonic ether) glycol poly-(1, the ammediol carbonic ether) glycol poly-(1,6-hexylene glycol carbonic ether) glycol 1, ammediol 1,4-butyleneglycol methylene radical-4,4 '-two (diphenyl diisocyanate) methylene radical-4,4 '-two (cyclohexyl isocyanates) ??865.50 ??905.00 ??1000.00 ??38.00 ??45.00 ??125.00 ??132.00 Shell?Chem.Co. Shell?Chem.Co. Bayer?Corp. Shell?Chem.Co. BASF Bayer?Corp. Bayer?Corp.
Embodiment 1
Tested the viscosity of polyvalent alcohol among the embodiment 1.It is found that the viscosity of PTMC 2000 is higher than the viscosity of Desmophen C-200 far away under the room temperature, this be since the rigidity carbonate group concentration of PTMC 2000 higher cause (table 2, Fig. 1).Viscosity with temperature significantly reduces.Because shorter (three CH of alkyl sequence 2Group), the second-order transition temperature that has been found that PTMC 2000 is 28.5 ℃, is six CH than alkyl sequence 2Obviously higher (58.3 ℃) of the Desmophen C-200 of group.
The viscosity of table 2 polycarbonate polyol
Viscosity mpa.s (cps)
Temperature (℃) ????PTMC?2000 ????Desmophen?C-200
????100 ????87 ????84 ????77 ????70 ????60 ????57 ????50 ????40 ????36 ????24 ????1750 ????2500 ????5450 ????8600 ????14600 ????69500 ????＞100000 ????400 ????490 ????660 ????750 ????1430 ????1860 ????5250 ????10900
Embodiment 2
Tested the consistency of chain extension agent and polyvalent alcohol among the embodiment 2.PTMC 2000 and chain extension agent (1,4-BD and 1,3-PDO) consistency between is by studying with specific mixed component under differing temps.The mixture that visual inspection obtains.The different % concentration of chain extension agent among contrast polyvalent alcohol and the PTMC 2000 have been tested under the room temperature, 70 ℃ and 90 ℃ respectively.In the room temperature to 90 ℃, PTMC 2000 and 1, the 4-butyleneglycol (1,4-BD) and 1, ammediol (1,3-PDO) compatible.In this test, the weight ratio of polyvalent alcohol and chain extension agent is the elastomerics of 22-35% corresponding to hard segment concentration.Under the room temperature, the consistency of Desmophen C-200 and chain extension agent is limited.The results are shown in the table 3.
The consistency of table 3 polycarbonate diol and chain extension agent
The % hard segment ??????????????22 ??????????????25 ??????????????28 ??????????????35
Temperature ℃ ????RT ????70 ????90 ????RT ????70 ????90 ????RT ????70 ????90 ????RT ????70 ????90
????1，3-PDO ????PTMC?2000 ????Desmophen?C-200 ????C ????PC ????C ????C ????C ????C ????C ????PC ????C ????C ????C ????C ????C ????PC ????C ????C ????C ????C ????C ????NC ????C ????C ????C ????C
????1，4-BD ????PTMC?2000 ????Desmophen?C-200 ????C ????PC ????C ????C ????C ????C ????C ????PC ????C ????C ????C ????C ????C ????PC ????C ????C ????C ????C ????C ????NC ????C ????C ????C ????C
C=is compatible; The PC=part is compatible; NC=is incompatible.
Embodiment 3
Among the embodiment 3, prepared hard segment concentration with single stage method and be respectively 22,25,28 and 35% TPUs.Before the elastomer production, with the vacuum-drying 24 hours at least under 70 ℃ of polyvalent alcohol and chain extension agent.Former state from supplier since the vulcabond is used.NCO% tests by titration according to Di-n-Butyl Amine method (ASTM D1638-74).Isocyanic ester coefficient (equivalence ratio of isocyanic ester and hydroxyl) is 1.02.Polyvalent alcohol and chain extension agent are weighed in plastic cup, and 100 ℃ or 135 ℃ of heating down.Benzoyl chloride is joined in polyvalent alcohol and the chain extension agent mixture.To under mixing temperature, join in polyvalent alcohol and the chain extension agent mixture by pre-heated vulcabond, and all components will acutely be mixed 5-10 second.Then mixture is poured on the mould of teflon coating, wherein this mould is heated to 105 ℃ or 135 ℃ in advance.When gel occurring, (determine), mould be placed on the Carver press according to Cheng Sifa, and with resin pressure be 165.5MPa (24,000psi), temperature is 105 ℃ or 135 ℃ of lower compression molds.Subsequently, with polyurethane sheet post-hardening 24 hours in 105 ℃ or 135 ℃ of baking ovens (perhaps 135 ℃ of sclerosis 20 hours and 150 ℃ of sclerosis 4 hours down).Post-hardening is not all to need.During preparation aromatics TPUs, sclerosis and post-hardening condition are listed in the table 4, and sclerosis and the post-hardening condition of preparation aliphatics TPUs are listed in table 13 and 14.One week of preparation back test polyurethane elastomer.
Sclerosis and post-hardening condition during table 4 preparation MDI-TPUs
PTMC?2000 Desmophen?C-200
Mixing condition curing condition post-hardening condition 135 ℃ of following 10 seconds 2 Benzoyl chlorides (1,4-BD) 4 Benzoyl chlorides (1,3-PBO) 135 ℃ (165.5MPa (24 in following 1 hour, 000psi) down extruding) 135 ℃ following 20 hours (1,4-BD) 135 ℃ following 20 hours 150 ℃ following 4 hours (1,3-PDO) 105 ℃ of following 5 seconds 105 ℃ of following 1 hour (following 24 hours of 105 ℃ of 165.5MPa (24,000lbs) down extruding)
Embodiment 4
Among the embodiment 4, tested based on PTMC 2000 and Desmophen C-200, and with 1,3-PDO increases prescription and the performance of the basic TPUs of MDI of chain.
Data are shown in table 5 and 6.Hard segment concentration is increased to 35% from 22%, causes PTMC 2000TPUs hardness to be increased to 91 Shore A from 73 Shore A.Under identical hard segment concentration, the hardness of Desmophen C-200 TPUs is low slightly.Usually, as was expected for tear strength for the tensile strength of TPUs, Young's modulus and breach (Die C), increases along with the increase of hard segment concentration.PTMC 2000 elastomeric wear resistancies are very good, are better than the wear resistance that is obtained by Desmophen C-200.This may be the enhancement owing to hydrogen bond in PTMC 2000 urethane, because contain a high proportion of carbonate group that can form hydrogen bond in this urethane.The wear resistance of PTMC 2000 TPUs is similar to or even is better than the wear resistance of PTMO 2000 and TONE polycaprolactone TPUs.Some example of PTMO2000 TPUs has for example 13 and 20 rub resistance coefficient.Referring to table 6-A, 17 and 18, comprising about performance data based on the TPUs of commercially available polyvalent alcohol.
PTMC TPUs demonstrates low relatively compression set (4-7%), is lower than the compression set (14.3-23.5%) of Desmophen C-200TPUs.Interesting is, 1, and the elasticity that 3-PDO increases the polycarbonate TPUs of chain increases along with the increase of hard segment concentration.
Table 5 is based on PTMC 2000/1, the physical and mechanical properties of the TPUs of 3-PDO/MDI
SPM-22 SPM-25 SPM-28 SPM-35
Hardness Shore A 73 83 88 91
Performance under the room temperatureTensile strength elongation Young's modulus stress (during 100% strain) stress (during 300% strain) toughness MPa(psi) ％ MPa(psi) MPa(psi) MPa(psi) MPa(psi) 23.7(3440.00) 738.20 5.7(823.30) 0.33(489.10) 7.2(1056.00) 75.4(10940.00) 0.84(2895.00) 560.60 9.2(1331.00) 5.2(751.90) 9.9(1436.00) 56(8116.00) 26.8(3885.00) 566.80 19(2755.00) 7.3(1066.00) 13.2(1925.00) 78.1(11330.00) 28.2(4091.00) 425.90 117.3(17020.00) 11(1590.00) 19.1(2771.00) 68.7(9970.00)
Performance in the time of 70 ℃Tensile strength, (changing %) elongation Young's modulus stress, (during 100% strain) stress, (during 300% strain) toughness Other performance under the room temperatureCompression set during 70 ℃ of split tear breach tearing resistance wearing and tearing * elasticity MPa (psi) % MPa (psi) MPa (psi) MPa (psi) MPa (psi) Kg/cm (1bs/in) Kg/cm (1bs/in) mg loss % % 11.1(1621.00) (-53) 1039.00 6.8(989.30) 2.3(327.10) 3.4(491.70) 62.2(9027.00) 15(83.94) 67.6(378.50) 2 6 4.00 13.2(1910.00) (-34) 777.00 12.6(1822.00) 3.3(482.50) 5.4(773.30) 72.2(10470.00) 18.7(104.70) 76.8(429.90) 7 9 6.00 15.9(2313.00) (-40) 873.30 14.9(2168.00) 3.6(523.30) 6.0(874.80) 72.5(10520.00) 15.7(88.01) 96.3(539.10) 4 12 4.30 17.7(2574.00) (-37) 741.70 41.9(6072.00) 6.2(894.90) 9.0(1311.00) 77.5(11240.00) 39.8(223.10) 128.5(719.60) 1 19 7.60
* 4000 circulations, 500gr, H22 wheel
Table 6 is based on Desmophen C-200/1, the physical and mechanical properties of the TPUs of 3-PDO/MDI
DPM-22 DPM-25 DPM-28 DPM-35
Hardness Shore A 64 70 78 82
Performance under the room temperatureTensile strength elongation Young's modulus stress (during 100% strain) stress (during 300% strain) toughness MPa(psi) ％ MPa(psi) MPa(psi) MPa(psi) MPa(psi) 24.4(3535.00) 838.00 5.5(794.00) 2.6(380.00) 4.9(717.30) 75.2(10900.00) 28.4(4116.00) 887.00 5.0(729.00) 3.4(493.70) 6.7(964.70) 100.7(14610.00) 44.3(6419.00) 899.00 8.8(1283.00) 3.9(566.30) 8.1(1170.00) 161.5(23420.00) 50(7246.00) 741.00 9.7(1411.00) 7.1(1034.00) 15.3(2218.00) 166.2(24110.00)
Performance in the time of 70 ℃Tensile strength, (changing %) elongation Young's modulus stress, (during 100% strain) stress, (during 300% strain) toughness Other performance under the room temperatureCompression set during 70 ℃ of split tear breach tearing resistance wearing and tearing * elasticity MPa (psi) % MPa (psi) MPa (psi) MPa (psi) MPa (psi) Kg/cm (1bs/in) Kg/cm (1bs/in) mg loss % % 12.0(1737.00) (-51) 989.00 4.0(579.60) 2.2(318.10) 3.8(545.40) 58.4(8463.00) 37.5(210.00) 52.9(296.00) 43 51 14.30 14.5(2105.00) (-49) 915.30 73.6(10680.00) 3.5(393.30) 4.7(678.50) 68.3(9902.00) 22.5(126.00) 61.4(344.00) 201 45 9.50 7.5(1094.00) (-83) 498.20 63.3(9180.00) 2.8(410.00) 4.7(682.20) 23.1(3349.00) 27.7(155.00) 74.4(417.00) 69 44 10.20 21.4(3101.00) (-57) 736.20 16.6(2412.00) 5.6(805.70) 8.7(1268.00) 84.3(12230.00) 42.5(238.00) 103.2(578.00) 199 36 23.50
* 4000 circulations, 500gr, H22 wheel
Table 6-A is based on the performance of the TPUs of commercially available polyvalent alcohol *
1 ?2 ?3 ?4
Prescription TONE PTMO 2,000 1,3-PDO 1,4-BD MDI hard segment hardness The % Shore A 54.51 1.94 13.38 22 58.8 ?49.30 ?1.99 ?11.94 ?22 ?58.2 ?96.52 ?4.28 ?24.20 ?22.8 ?73 ?97.04 ?3.63 ?24.33 ?22.4 ?71
The Tg of the compression set DSC test that the performance hot strength elongation Young's modulus split tear breach tearing resistance Taber abrasion index elasticity under the room temperature is 70 ℃ MPa(psi) ％ MPa(psi) Kg/cm(1bs/in) Kg/cm(1bs/in) ％ ％ ℃ 29.3(4253.00) 1048.00 68(383.20) 3.5 -42.81 ?28.3(4103.00) ?1074.00 ?65.8(368.60) ?3 ?-44.07 ?31.7(4600.00) ?1060.00 ?7.2(1040.00) ?23.7(133.00) ?57.3(321.00) ?13 ?64 ?12.10 ?31.3(4540.00) ?1080.00 ?6.8(985.00) ?21.8(122.00) ?57.5(322.00) ?20 ?63 ?10.60
* Evaluation of 1,3-Propanediol (PDO) in Polyurethane Applications (1, the applicating evaluating of ammediol in urethane) .Phase I:Polyurethane Elastomeres (polyurethane elastomer), P.Jackson, J.Wang, A Sendi jarevic, and K.C.Frisch, 1996
Embodiment 5
Among the embodiment 5, with 1, the 4-BD chain extension agent has prepared PTMC TPUs in hard segment concentration is the 22-35% scope, and has tested multiple performance.Data are shown in table 7 and 8.The strength property of PTMC 2000 and Desmophen C-200 TPUs (Young's modulus, Young's modulus and toughness when tensile strength, 100% and 300% strain) and breach tear strength are along with the increase of hard segment concentration changes very equably.The tensile strength that has been found that PTMC-TPUs is lower slightly than Desmophen C-200's, but the former modulus value but high slightly (Fig. 2 and 3).For example extension at break, modulus and elastic performance specification, 1,4-BD increases the TPUs of chain than 1, and it is more soft that 3-PDO increases the TPUs of chain.Find that once more the elasticity of PTMC TPUs increases along with the increase of hard segment concentration.
Table 7 is based on PTMC 2000/1, the physical and mechanical properties of the TPUs of 4-BD/MDI
SBM-22 SBM-25 SBM-28 SBM-35
Hardness Shore A 79(32D) 76(31D) 91(42D) 94(58)
Other performance breach tearing resistance elasticity under performance hot strength elongation Young's modulus stress (during 100% strain) stress (during 300% strain) the toughness room temperature under the room temperature MPa(psi) ％ MPa(psi) MPa(psi) MPa(psi) MPa(psi) Kg/cm(1bs/in) ％ 13.6(1974.00) 624.50 10.6(1533.00) 3.1(448.40) 5.2(748.10) 38.3(5551.00) 47.6(266.40) 4 11.4(1649.00) 601.70 4.9(708.60) 2.1(312.00) 4.3(630.20) 30.1(4374.00) 39.3(220.10) 12 20.1(2919.00) 578.70 30.3(4398.00) 5.3(771.40) 9.2(1331.00) 58.5(8488.00) 67.7(378.90) 13 35.5(5153.00) 502.20 67.2(9745.00) 10.1(1460.00) 18.9(2747.00) 91.4(13250.0) 114.7(642.10) 24
Embodiment 6
Among the embodiment 6, the stress-strain property when testing 70 ℃ is assessed elastomeric thermotolerance.Have been found that PTMC 2000/1, the reservation of the tensile strength of 3-PDO/MDI TPUs is than Desmophen C-200/1, what slightly high (referring to Fig. 4) of 3-PDO/MDI TPUs.The extension at break of PTMC 2000 obviously increases along with the increase of temperature, and Young's modulus then reduces (referring to table 5).Desmophen C-200/1, the poor heat resistance of 4-BD/MDI TPUs (referring to table 8).Thermal expansivity by the TMA test has been found that PTMC TPUs low (referring to table 9) than Desmophen C-200.For PTMC 2000, be 160 ℃-209 ℃ according to the softening temperature of the TPUs of TMA test, and be 160 ℃-175 ℃ for the softening temperature of the Desmophen C-200 urethane of correspondence.The softening temperature of Desmophen C-200 is subjected to the influence of chain extension agent not obvious.
Table 8 is based on Desmophen C-200/1, the physical and mechanical properties of the TPUs of 4-BD/MDI
DBM-22 DBM-25 DBM-28 DBM-35
Hardness Shore A 64 71 77 80
Performance under the room temperatureTensile strength elongation Young's modulus stress (during 100% strain) stress (during 300% strain) toughness MPa(psi) ％ MPa(psi) MPa(psi) MPa(psi) MPa(psi) 22.5(3257.00) 855.20 6.3(920.10) 2.7(392.40) 5.0(724.20) 77.6(11250.00) 25.4(3677.00) 853.90 7.5(1085.00) 3.4(492.70) 6.2(904.30) 93.1(13498.00) 34.6(5014.00) 870.60 8.6(1252.00) 4.0(584.80) 7.8(1135.00) 128.2(18587.00) 43.9(6361.00) 789.20 8.2(1189.00) 4.7(683.80) 5.9(856.90) 210.3(23501.00)
Performance in the time of 70 ℃Tensile strength elongation Young's modulus stress (during 100% strain) stress (during 300% strain) toughness Other performance under the room temperatureBreach tearing resistance elasticity MPa(psi) ％ MPa(psi) MPa(psi) MPa(psi) MPa(psi) Kg/cm(1bs/in) ％ 0.2(30.74) 73.28 39.0(5658.00) - - 0.2(29.54) 45.9(257.10) 54 12.2(1772.00) 865.00 5.0(721.00) 2.3(341.10) 3.7(539.70) 50.8(7365.00) 61.1(342.10) 42 18.8(2734.00) 1039.00 6.1(880.50) 2.7(384.90) 4.5(656.30) 89.2(12940.00) 72.8(407.80) 42 2.7(392.40) 121.30 19.7(2852.00) 3.4(488.60) - 3.0(433.50) 119.6(669.80) 33
* 4000 circulations, 500gr, H22 wheel
Embodiment 7
In embodiment 7, tested form.The second-order transition temperature of PTMC TPUs is about 0 ℃, when testing by DMA, is offset about 10 ℃.High relatively Tg makes that these urethane are more suitable for being higher than under the room temperature as having very good elastic elastic-plastic material.Low 30 ℃ approximately of the second-order transition temperatures of Desmophen C-200 TPUs.Also realized knowing clearly by FTIR spectrum to form.For the polycarbonate aromatic polyurethane, the bands of a spectrum in the elastomeric FTIR spectrogram are generally :-NH (free and bonding) is positioned at 3300-3400cm -1, CH 2Be positioned at 2900-2970cm -1, in the carbonic ether and the C=O that is keyed on the polyurethanyl group be positioned at 1740-1759cm -1, the C=O with the polyurethanyl group keyed jointing is not positioned at 1706cm -1, aryl is positioned at 1600cm -1, in the ether-C-O-C-is positioned at 1033cm -11705cm -1/ 1745cm -1Specific absorption increase along with the increase of hard segment concentration, the not increase of bonding polyurethane-base mass contg may be described.For PTMC TPUs, this ratio is higher.Between the polyurethanyl group, by bridging carbonic ether and polyurethanyl group and between polycarbonate polyurethane, form hydrogen bond.
Some form performance of table 9 TPUs
??Tg(DMA)(℃) ??Tg(DSC)(℃) ??Tm(TMA)(℃) Thermal expansivity (mm/m ℃)
?SPM-22 ?SPM-25 ?SPM-28 ?SPM-35 ?DPM-22 ?DPM-25 ?DPM-28 ?DPM-35 ????13.96 ????9.88 ????11.89 ????9.71 ????-28.34 ????-30.00 ????-31.60 ????-28.53 ????-1.12 ????0.36 ????0.19 ????2.88 ????-29.76 ????-31.54 ????-31.80 ????-30.32 ????159.86 ????201.97 ????206.67 ????208.64 ????175.01 ????161.10 ????169.47 ????162.02 ????123.00 ????87.20 ????231.00 ????149.00 ????426.00 ????281.00 ????224.00 ????219.00
Embodiment 8
Tested the water tolerance of PDO/MDI prescription among the embodiment 8.Water tolerance is to estimate by the increase of weight and the variation of stress-strain property after two weeks in 70 ℃ of water of test immersion.The results are shown in table 10 and 11 and Fig. 5 and 6 in.The weight of PTMC TPUs increases to 1.2-1.6%, Desmophen C-200 low slightly (0.8-1%).These results are relevant well with the variation of tensile strength, PTMC 2000 tensile strengths be changed to 8-57% (depending on hard segment concentration), and Desmophen C-200 tensile strength be changed to 3.6-33.5%.The water tolerance of Desmophen C-200 is more preferably owing to (six-CH on more hydrophobic structure 2Group).
Transparency is to test by the visible-range build-in test transmittance (%) in the 474-630 nanometer relatively.Transparency reduces along with the increase of hard segment concentration.Compare with Desmophen C-200, PTMC 2000 TPUs show obviously higher transparency under different hard segment concentration.This may be because the more unordered structure of PTMC skeleton or since soft chain segment and hard segment the blended degree is higher mutually causes.
Table 10 immersed in 70 ℃ of water for two weeks to PTMC 2000/1, the 3-PDO/MDI Effect on Performance
??SPM-22 ??SPM-25 ??SPM-28 ??SPM-35
?? Initial performanceTensile strength elongation Young's modulus stress (during 100% strain) stress (during 300% strain) toughness ??MPa(psi) ??％ ??MPa(psi) ??MPa(psi) ??MPa(psi) ??MPa(psi) ??21.5(3114.00) ??741.80 ??5.8(836.80) ??3.4(486.50) ??7.1(1037.00) ??71.7(10400.00) ??30.0(4355.00) ??685.20 ??7.9(1151.00) ??3.9(570.50) ??9.2(1334.00) ??83.5(12110.00) ??37.4(5423.00) ??675.60 ??8.8(1272.00) ??4.6(673.70) ??11.7(1693.00) ??105.4(15290.00) ??29.1(4216.00) ??396.30 ??11.5(1662.00) ??8.5(1235.00) ??22.0(3196.00) ??59.7(8659.00)
?? Immerse in 70 ℃ of water after two weeks?? PerformanceTensile strength, (changing %) elongation Young's modulus stress, (during 100% strain) stress, (during 300% strain) toughness ??MPa(psi) ??％ ??MPa(psi) ??MPa(psi) ??MPa(psi) ??MPa(psi) ??9.3(1342.00) ??(-56.9) ??572.70 ??5.1(737.50) ??2.4(353.70) ??4.9(712.90) ??28.8(4182.00) ??18.9(2757.00) ??(-36.7) ??712.90 ??5.2(754.90) ??3.0(428.30) ??6.6(958.90) ??60.8(8820.00) ??20.1(2986.00) ??(-44.9) ??625.60 ??4.9(711.30) ??3.5(503.50) ??8.4(1218.00) ??58.6(8505.00) ??31.5(4564.00) ??(8.2) ??541.70 ??8.0(1156.00) ??6.3(917.70) ??15.2(2202.00) ??79.9(11590.00)
Table 11 immersed in 70 ℃ of water for two weeks to Desmophen C-200/1, the 3-PDO/MDI Effect on Performance
DPM-22 DPM-25 DPM-28 DPM-35
Initial performanceTensile strength elongation Young's modulus stress (during 100% strain) stress (during 300% strain) toughness MPa(psi) ％ MPa(psi) MPa(psi) MPa(psi) MPa(psi) 16.6(2402.00?) 939.00 4.5(652.50) 2.4(338.50) 3.9(572.80) 71.3(10340.00) 27.6(4009.00) 1124.00 5.8(837.90) 2.7(394.70) 4.7(684.90) 120.9(17540.00) 21.8(3165.00) 910.10 8.3(1202.00) 3.4(500.40) 6.0(874.60) 90.0(13050.00) 33.6(4870.00) 730.80 11.5(1669.00) 5.9(862.00) 12.2(1772.00) 128.5(18640.00)
Immerse the performance after two weeks in 70 ℃ of waterTensile strength, (changing %) elongation Young's modulus stress, (during 100% strain) stress, (during 300% strain) toughness MPa(psi) ％ MPa(psi) MPa(psi) MPa(psi) MPa(psi) 17.4(2527.00) (5.2) 1070.00 3.2(460.60) 1.8(257.50) 3.1(450.70) 71.1(10320.00) 18.4(2664.00) (-33.5) 1065.00 4.6(664.10) 2.1(301.30) 4.0(581.60) 83.4(12100.00) 21.0(3051.00) (-3.6) 968.40 6.3(915.80) 2.7(398.40) 5.3(773.10) 90.4(13110.00) 37.0(5370.00) (10.2) 805.80 8.4(1217.00) 4.9(711.00) 9.8(1422.00) 124.5(18060.00)
Embodiment 9
Embodiment 9 has tested the chemical resistant properties of TPUs in multiple medium, and described multiple medium comprises oil (100% mesodialyte wax oil), Fisher Brand 19, ethylene glycol, diluted acid (10% sulfuric acid and 10% hydrochloric acid) and sodium hydroxide.The results are shown among table 12 and Fig. 7.Weight in the hydraulic efficiency oil increases little, and the weight increase is higher in the mineral acid, particularly for PTMC TPUs.Except the Desmophen C-200 under 35% hard segment concentration, the weight increase in the sodium hydroxide is low relatively.Be, increase that PTMC TPUs is well below Desmophen C-200TPUs unexpectedly for the weight in the ethylene glycol.In these media, the overall tolerability of TPU is good.For relatively, will be shown among the table 12-A based on the tolerance of the TPUs of polyoxy tetramethylene glycol (POTMG).
Chemical resistant properties under table 12 room temperature after one week of immersion
Oil Ethylene glycol 10% hydrochloric acid 10% sulfuric acid ?10％NaOH
Weight increases (%)
DPM?TPUs* DBM?TPUs* SPM?TPUs* ?0.0-0.32 ?0.0-0.28 ?0.15-0.31 ?1.00-1.26 ?0.90-0.92 ?0.39-0.63 ?0.22-0.83 ?0.22-0.44 ?0.80-1.51 ?0.14-0.53 ?0.00-0.58 ?0.66-1.52 ?0.0-1.10 ?0.35-0.48 ?0.00-0.58
* hard segment concentration is 22%-35%.
Show 12-A based on POTMG 1000/1,4-BD/MDI, the TPUs of 35% hard segment concentration immerses the tolerance * after the week
Weight increases %
????H 2SO 4, 30% NaOH, 10% ethylene glycol oil ??1.1 ??1.6 ??41.4 ??3.1
*Reactivity?Studies?and?Cast?Elastomers?Based?onTrans-cyclohexane-1，4-Diisocyanate?and?1，4-PhenyleneDiisocyanate，S.W.Wong?and?K.C.Frisch，Advances?in?UrethaneScience?and?Technology，Vol，8，Page?74(1981)
Embodiment 10
Among the embodiment 10, hardened based on alicyclic diisocyanate H 12The TPUs of MDI and PTMC 2000.Curing condition is shown in table 13 and 14.In the capable symbol of each table the first, SPH-25 to SPH-35 is the PTMC 2000/1 of 25-35% corresponding to hard segment concentration, 3-PDO/H 12MDI.SBH-25 to SBH-35 is the PTMC2000/1 of 25-35% corresponding to hard segment concentration, 4-BD/H 12MDI.
The tensile strength that increases along with hard segment concentration is a medium value, and with 1,3-PDO compares with 1,4-BD chain extension agent high slightly.For PTMC 2000TPUs, regardless of being with MDI or using H 12MDI, with 1,3-PDO is than with 1, and the 4-BD chain extension agent shows better properties.Should be pointed out that owing to lower green strength H 12MDI TPUs is lower than MDI TPUs stiffening temperature.
Second-order transition temperature is by dsc and dynamic mechanical method test.H 12The DSC second-order transition temperature of MDI TPUs is lower than 0 ℃ slightly, lower than MDI base TPUs, this explanation, soft chain segment and H 12The interaction of MDI still less.H 12The softening temperature of MDI is generally 175 ℃-193 ℃.1, the TPUs that 3-PDO increases chain is transparent under 25% hard segment concentration, and is translucent under the 28%-35% hard segment concentration.1, the TPUs that 4-BD increases chain is translucent under 25% hard segment concentration, is muddy under higher hard segment concentration.As reference, will be based on H 12MDI/PTMO 2000/1, and some performance of the TPUs of 4-BD is listed among the table 13-A.
SPH-TPUs is immersed in that the changes in weight after two weeks is 1.2-1.73% in 70 ℃ of water, is similar to MDI-TPUs (referring to table 15).
Increase the H of test by weight 12The tolerance of MDI-TPUs in hydraulic efficiency oil, ethylene glycol, 10% hydrochloric acid, 10% sulfuric acid and 10%NaOH is shown in Table 16.Oil-proofness excellence (not having weight to increase).Weight in acid, sodium hydroxide, particularly ethylene glycol increases higher.
Table 13 is based on PTMC 2000/1,4-BD/H 12The prescription of the TPUs of MDI and performance
?SBH-25 ?SBH-28 ?SBH-30 ?SBH-35
PrescriptionPTMC 1，4-BD H 12MDI T-12 gr gr gr ％wt ?29.23 ?1.06 ?9.16 ?0.0065 ?27.97 ?1.96 ?10.05 ?0.0075 ?27.14 ?2.20 ?10.64 ?0.0075 ?24.46 ?2.73 ?12.79 ?0.0075
ProcessingMixing temperature mold sclerosis post-hardening hard segment concentration hardness ℃ ℃/hour ℃/hour % Shore ?135 ?135/1 ?85/24 ?25 ?68 ?135 ?135/1 ?85/24 ?28 ?84 ?135 ?135/1 ?85/24 ?30 ?86 ?135 ?135/1 ?85/24 ?35 ?88
Performance under the room temperatureTensile strength elongation Young's modulus stress (during 100% strain) stress (during 300% strain) breach tearing resistance MPa(psi) ％ MPa(psi) MPa(psi) MPa(psi) Kg/cm(1bs/in) ?4.6(660.50) ?751.60 ?6.8(985.10) ?1.9(275.10) ?2.9(425.50) ?43.6(244.10) ?11.8(1706.00) ?435.00 ?17.7(2545.00) ?1.9(282.30) ?4.8(697.00) ?53.8(301.10) ?23.5(3405.00) ?433.70 ?26.8(3892.00) ?7.4(1075.00) ?15.1(2189.00) ?71.9(402.80) ?9.5(1371.00) ?336.10 ?6.8(982.60) ?0.3(46.30) ?- ?65.1(364.60)
Thermal characteristicsTg (DMA) Tg (DSC) Tm (TMA) thermal expansivity outward appearance ℃ ℃ ℃ μm/m℃ 5.06-4.37 96.22 161.00 is translucent 3.61-6.26 193.03-44.00 muddinesses 5.24-6.13 184.00-426.00 muddinesses 7.89-3.29 180.47 247.00 muddinesses
Show 13-A based on PTMO/1,4-BD/H 12The performance * of the TPUs of MDI
?I-1.0 ?I-1.5 ?I-2.0
Performance tensile strength elongation Young's modulus under the hard segment hardness room temperature % Shore MPa (psi) % MPa (psi) ?24.9 ?65 ?28.3(4106.00) ?1146.00 ?4.0(574.00) ?29.7 ?74 ?27.9(4046.00) ?1058.00 ?4.9(712.00) ?34.2 ?79 ?21.8(3164.00) ?873.00 ?6.7(970.00)
*Structure-Property?Relationships?of?Transparent?Aliphatic?Polyurethane?Elastomers?from?theGeometric?Isomers?of?Methylene?Bis(4-Cyclohexyl?Isocyanate)，S.Wong，K.C.Frisch，C.A.Byrne，D.P.Mack，and?N.S.Schneider，Advances?in?Urethane?Science?and?Technology，Vol?9，page?77，1984.
Table 14 is based on PTMC 2000/1,3-PDO/H 12The prescription of the TPUs of MDI and performance
SPH-25 SPH-28 SPH-30 SPH-35
PrescriptionPTMC?2000 1，3-PDO H 12MDI T-12 gr gr gr ％wt 29.92 1.25 8.81 0.008 30.00 1.61 10.29 0.008 28.80 1.96 10.91 0.008 26.00 2.78 12.45 0.008
ProcessingMixing temperature mold sclerosis post-hardening hard segment concentration hardness ℃ ℃/hour ℃/hour % Shore 135 135/1 100/24 25 68 135 135/1 90/24 28 75 135 135/1 90/24 30 78 135 135/1 100/24 35 89
Performance under the room temperatureTensile strength elongation Young's modulus stress (during 100% strain) stress (during 300% strain) breach tearing resistance MPa(psi) ％ MPa(psi) MPa(psi) MPa(psi) Kg/cm(1bs/in) 12.9(1889.00) 603.30 7.4(1075.00) 3.2(459.00) 5.6(835.00) 51.4(288.10) 19.5(2830.00) 455.10 8.7(1258.00) 4.8(701.00) 11.7(1693.00) 59.2(331.60) 20.7(3088.00) 448.70 11.0(1601.00) 6.1(885.80) 13.1(1912.00) 63.4(355.30) 20.7(3008.00) 294.20 40.7(5907.00) 9.7(1401.00) - 84.7(474.20)
Thermal characteristicsTg (DMA) Tg (DSC) Tm (TMA) thermal expansivity outward appearance ℃ ℃ ℃ μm/m℃ 9.20 0.88 181.42-44.80 is transparent 10.72-0.87 185.81 100.00 is translucent 10.78-3.84 174.96 210.00 is translucent 7.34-1.85 179.09 139.00 is translucent
Table 15 immerses the changes in weight after two weeks in 70 ℃ of water
Initial weight (g) Final weight (g) Changes in weight (%)
????SPH-25 ????SPH-28 ????SPH-30 ????SPH-35 ????0.1860 ????0.1305 ????0.1925 ????0.2025 ????0.1882 ????0.1327 ????0.1952 ????0.2087 ????1.20 ????1.72 ????1.42 ????1.73
Chemical resistant properties under table 16 room temperature after one week of immersion
Oil Ethylene glycol 10% hydrochloric acid 10% sulfuric acid ??10％NaOH
Changes in weight (%)
SPH?TPUs *SPH?TPUs * ????0.0 ????0.0 ??1.20-2.30 ??2.30-3.33 ??1.26-2.00 ??0.70-1.00 ??1.20-1.70 ??0.80-1.00 ??1.26-2.35 ??0.86-1.00
* hard segment concentration is 25%-35%.
Table 17 hard segment concentration is to the influence based on the TPUs hardness of PTMG 2000
????2PTMG20 ????3PTMG20
Hard segment concentration % hardness Shore A Shore D ????22 ????70 ????33 ????33 ????85 ????38
* M.Vlajic, E.Torlic, A.Sendijarevic, and V.Sendi jarevic, Polimeri, Vol 10 (3), 62-66 page or leaf, 1989.
Table 18 hard segment concentration is to the * that influences based on the TPUs hardness of CPL 2000
????2CPL20 ????3CPL20 ????4CPL20
Hard segment concentration % hardness Shore A Shore D ????22 ????72 ????33 ????32 ????82 ????39 ????39 ????89 ????44
* M.Vlajic, E.Torlic, A.Sendijarevic, and V.Sendi jarevic, Polimeri, Vol 10 (3), 62-66 page or leaf, 1989.

Claims (10)

1. a Polyurethane Thermoplastic Elastomer (TPU) composition comprises:
A) as poly-(propylene carbonate) glycol (PTMC glycol) of soft chain segment;
B) vulcabond; With
C) at least a dibasic alcohol, it and di-isocyanate reaction form the hard segment that accounts for composition 10-55% weight, and wherein, hard segment is defined as and the vulcabond of diol reaction and the summation of unreacted dibasic alcohol part.
2. according to the composition of claim 1, wherein the molecular weight of poly-(propylene carbonate) glycol is 300-6000.
3. according to the composition of claim 2, wherein the molecular weight of poly-(propylene carbonate) glycol is 1000-3000.
4. according to claim 1,2 or 3 composition, wherein the functionality of poly-(propylene carbonate) is about 2.
5. according to claim 1,2,3 or 4 composition, the amount of the hard segment of wherein sneaking into is 10-50% for making its concentration.
6. according to the composition of claim 5, the amount of the hard segment of wherein sneaking into is 20-40% for making its concentration.
7. each composition in requiring according to aforesaid right, wherein the dibasic alcohol in the hard segment is selected from aliphatic series, alicyclic, aralkyl and aromatic diol.
8. according to the composition of claim 7, wherein dibasic alcohol is selected from ethylene glycol, propylene glycol, 1, ammediol, the 2-methyl isophthalic acid, ammediol, 2,4-dimethyl-2-ethyl hexane-1,3-glycol, 2,2-dimethyl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 2-ethyl-2-isobutyl--1, ammediol, 1,3 butylene glycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 2,2,4-trimethylammonium-1, the 6-hexylene glycol, the sulphur di-alcohol, 1, the 2-cyclohexanedimethanol, 1, the 3-cyclohexanedimethanol, 1, the 4-cyclohexanedimethanol, 2,2,4,4-tetramethyl--1,3-cyclobutanediol and to xylenediol, or their mixture.
9. composition according to Claim 8, wherein dibasic alcohol is selected from 1, ammediol and 1,4-butyleneglycol, or their mixture.
10. each composition in requiring according to aforesaid right, wherein vulcabond is selected from aromatics, aliphatic series or alicyclic diisocyanate.
CNB018084109A 2000-03-27 2001-03-27 Thermoplastic polyurethane elastomers (TPUs) prepared with polytrimethylene carbonate soft segment Expired - Fee Related CN1177880C (en)

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US6852823B2 (en) 2002-08-09 2005-02-08 E. I. Du Pont De Nemours And Company Polyurethane and polyurethane-urea elastomers from polytrimethylene ether glycol
JP4542347B2 (en) * 2003-01-27 2010-09-15 大日精化工業株式会社 Thermoplastic polyurethane and use thereof
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JP6577940B2 (en) * 2013-06-04 2019-09-18 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Soft thermoplastic polyurethane elastomer and method for producing the same
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